Photographic silver halide elements having magenta-colored coupler dyes

ABSTRACT

WHEREIN X is an alkyl group or a halogen group, Y is a -COdivalent radical or an -SO2- divalent radical, R1 is an alkyl group having one to 18 carbon atoms, A is an -NR2SO2-divalent radical in which R2 is an alkyl group having one to 18 carbon atoms, and R3 is an aryl group.   Photographic elements are shown which contain coupler dyes of the general formula:

United States Patent Guzziet al.

3,647,468 Mar. 7, 1972 [54] PHOTOGRAPHIC SILVER HALIDE ELEMENTS HAVING MAGENTA- COLORED COUPLER DYES Alberto Guzzi; Remo Magagnoli, both of [72] Inventors:

Fcrrnnia; Lorenzo Vltmre, Pietra Ligure,

ull ni' llnly [73l Assignec: Smicifl per Azimli l errnnlu. Milan. Italy [22] Filed: May 14, 1968 [21] Appl.No.: 728,887

[30] Foreign Application Priority Data May 15, 1967 Italy ..800,361

[52] [1.5. CI ..96/l00, 96/9, 96/56.1 [51] Int. Cl ..G03c 1/40 [58] Field of Search ..96/9, 55, 100, 56.1

[56] References Cited UNITED STATES PATENTS 2,350,138 5/1944 Weissberger ..96/100 2,428,054 9/1947 Vittum et al..... ..96/9 2,455,169 11/1948 Glass et a1 ..96/9 3,408,194 10/1968 Loria ...96/l00 FOREIGN PATENTS OR APPLICATIONS 1,067,397 5/1967 Great Britain Jib/9 Primary Examiner.l. Travis Brown Attorney-Kinney, Alexander, Sell, Steldt & Delahunl 57 ABSTRACT Photographic elements are shown which contain coupler dyes of the general formula:

K wherein X is an alkyl group or a halogen group, Y is a -CO divalent radical or an SO2 divalent radical. R is an alkyl group having 1 to 18 carbon atoms. A is an NR-;SO2 diyalent radicjlin which R2 is an alkyl group mew: LL and 522 an 1 999:

.2 C loe, N". P9149 5? PHOTOGRAPHIC SILVER HALIDE ELEMENTS HAVING MAGENTA-COLORED COUPLER DYES It is known that photographic color images may be obtained by the reaction of certain chemical compounds, referred to as couplers or color formers, with the oxidation products of aromatic primary amine developers. The subtractive system of color formation commonly employs photographic images represented by the colors cyan, magenta and yellow, these colors being complementary to the three regions of spectral sensitization of photosensitive layers contained within photographic elements.

Cyan couplers commonly are phenyl or naphthol derivatives, magenta couplers are usually pyrazolone or cyanoacetyl derivatives, and yellow couplers are normally compounds in which a methylene radical directly links to two carbonyl groups. The dyes resulting therefrom by coupling are of the azomethine, indoaniline or indophenol class, depending on the coupler and developer compounds, Dyes of this type frequently exhibit poor light transmission characteristics (nonfaithful color reproduction) and unsatisfactory heat and light stability.

Ideal dyes should absorb only one of the primary colors and should freely transmit the two other primary colors. For example, cyan dyes should absorb only red light and should freely transmit green and blue-violet light. In addition, such spectral characteristics should be retained for long periods of time and should be resistant to light and to reasonably high temperatures.

The use of colored masks which automatically form during the color development process has been proven useful in improving the color efficiency of certain photosensitive materials. These masks are obtained, for example when azo-type colored couplers are employed in place of colorless couplers. Couplers of an alpha-naphthol type, for example, produce negative cyan images on a colorless background by color development. Also, 4-aryl-azo-l-naphthol type couplers, however, produce negative cyan images superimposed upon yellow, orange-red or magenta positive images formed by the residual azo dye.

Magenta colored couplers, rather than orange or yellow colored cyan couplers, are desired for correcting unsatisfactory absorption characteristics of cyan images. Such couplers should absorb green rather than blue light, and should freely transmit red light.

The difficulties in achieving these results are known. The positions of the absorption peaks of dyes of the 4-aryl-azo-lnaphthol class are greatly dependent upon the substituents of the aryl residue linked by an azo group to the naphthalene nucleus. Electron-attracting substituents in the latter aryl radical, particularly in a position ortho to the azo group, generally impart a bathochromic effect. Red or magenta dyes can thus be obtained with substitutions of the following type:

wherein R is a COOH group, a SO H group, a COOR' group, or a COR group wherein R is an alkyl group. However, COOH and -SO H substituents are detrimental for certain colored couplers which are intended to be applied by a dispersion technique. In this technique, water insoluble couplers are dissolved in certain high-boiling organic solvents, such as triphenyl phosphate or dibutyl phthalate, and are introduced into photographic emulsions as gelatin dispersions. Couplers which contain free carboxylic acid or sulfonic acid groups would not be readily soluble in such organic solvents, compromising the use thereof.

The COOR and COR substituents referred to above have been considered in French Pat. No. 1,247,973. The colored couplets thus obtained are soluble in the above organic solvents and the absorption peaks of these couplers are shifted toward longer wavelengths. Such couplers, however, exhibit poor stability. For example, a sample of developed photographic material containing a colored coupler of the above French patent in the form of a dispersion in dibutyl phthalate was conditioned at 90.0 C. for 24 hours, at a relative humidity of percent. The original red or magenta color was found to have been replaced by an orange-yellow color, rendering the dye ineffective for the intended purposes.

It has now been found that colored couplers of the class described below have favorable absorption characteristics, i.e., they are magenta colored and exhibit satisfactory resistance to elevated temperature and humidity conditions.

The colored couplers of the present invention are characterized by the following general formula:

CONE- wherein X is an alkyl group or a halogen group; Y is a -CO group or a SO group R, is an alkyl group having one to radical or a radical wherein B is a hydrogen atom, an alkyl group, a carbalkoxy group or a halogen group and D is a hydrogen atom, an alkanoyl group or a carbalkoxy group. Most preferably, B and D are COCH groups or -COOCH groups.

The colored couplers of the present invention have exhibited high reactivity in the color development process, the azo group in the position para to the naphthol hydroxy group being replaced by the oxidized developer to yield an indophenol-type cyan dye. The high reactivity, strong absorption in the green spectral zone (due to the particularly marked bathochromic effect), and resistance to heat and humidity effects, make this class of compounds particularly useful in the field of color photography.

Examples of colored couplers of this class are the following:

l N ll 0 CuHra C 3 @rzorsm-Q I SOzCm aa N I CH N S O2 COCHa 11 OH CH:

CONH- I N S O2CzC1a aa II N $0 COOOHa u an- OOCH:

1 2) 0H 01 CONH- I N S 02- II N COOCHu I SOzN- H COO Clix I 13 0H 01 fiOONH 0cm N G 0000113 I S O N- Cls aa 000C113 The colored couplers of the present invention may be prepared by reacting suitable aryldiazonium salts with certain alpha-naphthol compounds. Couplers 1, 2, 3, 4 and 5 were obtained by this method from l-hydroxy-2-(2-methyl-5'-lauroyl) naphthanilide and aryldiazonium chlorides. the latter being obtained by diazotization of the aniline compounds illustrated in the following Table A.

TABLE A.-ANILINE COMPOUNDS General Formula lnN--Ns 02-1u Corre- Meltlng sponding Crystalpolnt coupler lization R C.) number solvent (I) 113115 1 Ethano1.

(II) 135136 2 D0.

(III) Q 106-108 3 D0.

0 O CH:

(IV) @i) 169-170 4 D0. v1 01 121-122 5 Do.

1 C 0 CH3 By way of illustration, a typical process for the preparation of colored coupler No. 4 is given below. Colored couplers, 1, 2,3 and 5 were prepared in a similar manner from l -hydroxy-2-(2 -methyl-5-lauroyl)-naphthanilide.

PREPARATION OF COUPLER 4 a. 4-nitro-2-naphthalenesulfonanilide 55.2 g. of p-nitroaniline, 45.2 g. of beta-naphthalene sulfonyl chloride and 260 ml. of dry toluene were heated together for 3 hours. The solvent was then removed under vacuum and the residue was boiled, first with water, then with 1,500 ml. of a dilute solution of hydrochloric acid (1 part by volume of concentrated acid to 7 parts by volume of water).

The residue was boiled again in fresh dilute acid solution as above, and the product, separated by filtration, was dried and recrystallized from benzene. The melting point was 170-1 71 C. b. N-methyl-4'-nitro-2-naphthalenesulfonanilide 30.5 g. of sulfanilide (a) were suspended in 300 ml. of water. Thirty ml. of 30 percent sodium hydroxide solution were added to cause solution of the compound, which reprecipitated almost immediately as the sodium salt. Within a 30 minute period, ml. of dimethyl sulfate were added with stirring. During this period, portions of 30 percent sodium hydroxide solution were added to maintain the pH of the suspension between 8 and 9. A total of ml. of the sodium hydroxide were added. Thereafter, stirring was continued for an additional 15 minutes. The product was filtered under reduced pressure, washed with water, and after drying was recrystallized from acetic acid. 24.5 g. of product melting at l37-138 C. were obtained.

c. 4-amino-N-methyl-Z-naphthalenesulfonanilide A solution of 24.5 g. of nitro derivative (b) in 215 ml. of ethanol was refluxed and 43 g. of powdered iron were added in small portions. The exotherm of the reaction was sufficient to maintain boiling without external heating. After the addition of the powdered iron, the reaction mixture was refluxed for an additional one-half hour and was then filtered. The filtrate was poured into ice water and the product which separated was recovered by filtration, washed with water and dried. Upon crystallization from ethanol, 16.7 g. of product melting at 168-l 70 C. were obtained. (1. Colored Coupler 4 I 6.24 g. of the amine (c) in a solution containing 8 ml. of concentrated HCl and 36 m1. of water were diazotized at C. by addition ofa solution of 1.48 g. of sodium nitrite in ml. of water. The resultant diazonium salt solution was slowly added to a solution of 2-methyl-5 '-1auroyl-1-hydroxy-2- naphthanilide (8.26 g. in 230 ml. of pyridine), the temperature of the mixture being maintained below 5 C. The reaction mixture was allowed to stand overnight, the temperature of the mixture rising slowly to ambient temperature. The mixture was then poured, with stirring, into 1,200 ml. of water and the dye which separated was recovered by filtration. The dye was thoroughly washed, dried, and crystallized from 180 ml. of

acetone. 12.9 g. of colored coupler melting at 9396 C. were obtained.

The colored couplers 6, 7, 8, 9, and 10 were similarly obtained by replacing the 1-hydroxy-2-(2-methyl-5'-lauroyl)- naphthanilide with an equivalent amount of l-hydroxy-2-(2'- methyl-5-cetyl su1fony1)-naphthanilide. These compounds have both been described in applicants US Pat. application,

Ser. No. 701,995.

The p-acetylbenzenesulfonyl chloride and 2-chloro-5- acetylbenzenesulfonyl chloride intermediates used in preparing colored couplers 3, 5, 8 and 10 are referred to in the following literature: D. Bellone, U. Chittolini, A. Guzzi, Annali di Chimica, Rome, Vol. 54, pp. 510 et seq. The couplers, l l, 12 and 13 were prepared as follows:

COUPLER l 1 a. N'-hexadecyl-N'-[3', 5'-bis(carbomethoxy)phenyl]- sulfanilamide was prepared according to F. Coles (German Pat. No. 1,073,308). b. Colored Coupler 1 l 1 1.7 g. of amine (a) in a solution of 8 ml. of concentrated hydrochloric acid and 24 ml. of water were diazotized at 5 C. by the addition ofa solution of 1.48 g. of sodium nitrite in 10 ml. of water. This diozonium salt was obtained as a suspension. After removal of excess nitrous acid with sulfamic acid, the suspension was slowly added to a solution of 2'-methyl-5- cetylsulfonyl-1-hydroxy-2-naphthani1ide in 250 ml. of pyridine at 5 C. The mixture was stirred for an additional 6 hours, and was then allowed to stand overnight at room temperature. The mixture was poured, with stirring, into 1,200 m]. of water, causing the precipitation of the colored coupler which then was filtered, washed, dried and recrystallized from 220 ml. of acetone. 9.2 g. of Coupler 11, melting at 80-83 C. were thus obtained.

COLORED COUPLER l2 1 1.7 g. of the amine used in preparation of coupler 1 l were 5 lowed to stand overnight at room temperature and then was poured into 1,300 ml. of water. The coupler which separated was filtered, washed thoroughly with watervand, after drying, was crystallized from 300 ml. of acetic acid. The melting point was l76-179 C.

COLORED COUPLER 13 19.6 g. of the amine employed in preparation of couplers l 1 and 12 were diazotized as described above with 2.46. g. of

15 sodium nitrite. The suspension of diazonium salt was added,

under the conditions described for coupler 1 1, to a solution of 10.19 g. of l-hydroxy-2(2'-chIoro-5-acetyl)-naphthanilide in 300 ml. of pyridine. After standing overnight, the mixture was poured into 2,000 m1. of water. The product was recovered, dried, crystallized from 850 ml. of ethyl acetate, and recrystallized from 185 ml. of dioxane. The melting point was 21221 4 C.

Table B presents the properties and analytical data of the colored couplers described above.

The following examples are presented for illustrative purposes only, and should not be construed as limiting the scope of this invention:

EXAMPLE 1 3.6 g. of colored coupler 1 were dissolved in a mixture containing 7.2 m1. of dibutyl phthalate and 21.6 ml. of ethyl acetate by heating in a boiling water bath. The resulting clear solution was poured into 72 m1. of a 4 percent gelatin solution 35 containing 7.2 ml. of a 10 percent solution of sodium tetradecyl sulfate. The mixture was dispersed in a homogenizer at a temperature of about 40 C. The dispersion thus obtained was added to 1 kg. of a silver halide photographic emulsion sensitized to red light. This emulsion was spread on a transparent support and dried. The resulting photosensitive material was exposed and then processed'in a diethyl-p-phenylene diamine color developing bath. After bleaching and fixing and after drying, a cyan colored negative image of the subject and a magenta colored positive masking image were obtained.

EXAMPLE 2 4.7 g. of colored coupler 13 were dispersed in gelatin by the method of Example 1 using the following materials: 9.4 ml. of dibutyl phthalate; 28.2 ml. of ethyl acetate; 94 ml. of 4 percent gelatin and 9.4 ml. of 10 percent sodium tetradecyl sulfate. A photosensitive element was prepared therefrom by the procedure of Example 1. The photographic element was exposed, developed, bleached, fixed and dried, as described in Example 1. A cyan colored negative image of the subject, and a magenta colored positive masking image were obtained. A sample of the exposed and processed material was then conditioned for 24 hours at 90 C. and 75 percent RH. Upon examination the magenta colored image did not show Dioxine and ethyl acetate changes in color in tone and intensity.

A similar treatment, performed on a photographic element of the same type which contained one of the colored couplers of the above-mentioned French patent caused the positive image, initially magenta, to become yellow-orange in color. The absorption peak of this dye, determined on the photographic element itself, shifted from 507 to 485 mu; whereas in the case of the material containing the coupler l3, the peak remained at the same value of 508 mp. even after the conditioning step.

EXAMPLE 3 One gram of colored coupler l was dissolved in a heated mixture of 2 g. of n-butyl-myristoylamide and 6 ml. of ethyl acetate. This solution was added, with vigorous stirring, to 20 ml. of 4 percent inert gelatin solution containing 2 ml. of 10 percent sodium diethyl sulfosuccinate, The mixture was then homogenized at a temperature of 40 C. After homogenization, the total volume of the dispersion was increased to 50 ml. with water. 37.5 ml. of this dispersion were added to 100 g. of red-sensitized silver halide emulsion. Thereafter, 40 ml. of a similarly prepared dispersion of the colorless coupler lhydroxy-2(2-methyl-5'-lauroyl) naphthanilide were added. The resulting emulsion was spread on a transparent support, dried and light exposed. After color development in a developer containing 2-methyl-4-( N-ethyl-N-betamethanesulfonamidoethyl)-amino-aniline, bleaching, fixing and drying, a cyan colored negative image and a magenta colored positive masked image were obtained.

What is claimed is:

l. A silver halide photographic element having at least one colored coupler of the formula N Y-R1 group in which B is a hydrogen atom, an alkyl group, a carbalkoxy group or a halogen group, and D is a hydrogen atom, an alkanoyl group, or a carbalkoxy group.

4. A photographic element comprising a support and at least one silver halide emulsion layer having dispersed therein at least one colored coupler of the formula CONH wherein X is an alkyl group or a halogen group, Y is a CO divalent radical or an --SO divalent radical, R, is an alkyl group having one to 18 carbon atoms, A is an NR SO divalent radical wherein R is an alkyl group having one to 18 carbon atoms, and R is an aryl group.

5. A photographic element according to claim 4 wherein R,, is a naphthyl group.

6. A photographic element according to claim 4 wherein R group in which 8 is a hydrogen atom, an alkyl group, a carbalkoxy group or a halogen group and D is a hydrogen atom, a carbalkoxy group or an alkanoyl group.

7. A photographic element according to claim 4 wherein said at least one colored coupler is contained within a dispersed phase, said dispersed phase comprising a solution of said at least one colored coupler in a high-boiling organic solvent.

8. The element of claim 1 wherein said coupler has the formula l om-N-sm-Gom 10. The eIemEBYEfEIAiMi wherein said coupler has the formula OH CH3 CONH- I O0 CnHra 3 ,647,468 1L. W 1.. 12w.

1]. The element of claim 1 wherein said coupler has the for- 12. The element of claim I wherein said coupler has the formula mula 1 1H JOOnHza lo II 11 2:

COOH;

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION r ent No. 3,647, 68 Dated March 7, 1972 vIi1-rentor(s)Alberto Guzzi Remo Magagnoliand Lorenzo Vittore It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

OH OH Column L, line 1, v should read Column 5, line 1, H H should read OH Column 5, line 26, CH CH should read Column 6 line 21, under heedin "Melting Point (C 35-136 should read IBM--13 Column 8, line 79, Table B, DiOXine shQuld read Dioxane Signed and sealed this 5th day of December 1972..

(SEAL) Attest:

EDWARD M.FLETCHER,JR. 1 ROBERT GOTI'SCHALK Attesting Officer Commissioner of Patents FORM PO 105O (10-69) USCOMM'DC 6O376-P69 U 5, GOVERNMENT PRINTING OFFICE: I969 O-366-334 

2. A photographic element of claim 1 wherein R3 is a naphthyl group.
 3. A photographic element of claim 1 wherein R3 is a group in which B is a hydrogen atom, an alkyl group, a carbalkoxy group or a halogen group, and D is a hydrogen atom, an alkanoyl group, or a carbalkoxy group.
 4. A photographic element comprising a support and at least one silver halide emulsion layer having dispersed therein at least one colored coupler of the formula
 5. A photographic element according to claim 4 wherein R3 is a naphthyl group.
 6. A photographic element according to claim 4 wherein R3 is a group in which B is a hydrogen atom, an alkyl group, a cArbalkoxy group or a halogen group and D is a hydrogen atom, a carbalkoxy group or an alkanoyl group.
 7. A photographic element according to claim 4 wherein said at least one colored coupler is contained within a dispersed phase, said dispersed phase comprising a solution of said at least one colored coupler in a high-boiling organic solvent.
 8. The element of claim 1 wherein said coupler has the formula
 9. The element of claim 1 wherein said coupler has the formula
 10. The element of claim 1 wherein said coupler has the formula
 11. The element of claim 1 wherein said coupler has the formula
 12. The element of claim 1 wherein said coupler has the formula 